The goal of this work is the designed discovery, development and understanding of reactions which will substantially improve synthetic methodology. The proposed studies range from approaches which could provide new strategies for synthesis to the development of emerging methodology and the understanding of established reactions. The synthetic studies focus on the chemistry of organolithium reagents and include the formations and reactions of alpha-lithioamine synthetic equivalents, of beta-lithioamides and of lithiated aromatics. A systematic study of the structural requirements of lithiations directed to sites remote from the directing function will also be carried out. In addition, investigations of the ene reaction will be pursued. The proposed synthetic studies are applicable to the syntheses of many classes of molecules. In mechanistic work studies which will provide understanding of the mechanism of halogen-lithium exchange and of oxygen transfer reactions are proposed. These studies will provide knowledge which should be applicable to the improvement of current synthetic methodology.